Process of making permanent-press fabrics and garments



United States Patent Office 3,497,471 Patented Feb. 24, 1970 3,497,471 PROCESS OF MAKING PERMANENT-PRESS FABRICS AND GARMENTS Sidney Cohen, Hillsdale, Thaddeus A. Gulakowski, Ridgefield, and Phillip Adams, Murray Hill, N.J., assignors to Millrnaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Dec. 6, 1967, Ser. No. 688,327 Int. Cl. C08g 9/08, 9/18 US. Cl. 260-70 4 Claims ABSTRACT OF THE DISCLOSURE A process for treating fabrics to provide permanentpress pleats, creases, etc., while maintaining soft hand and good color fastness, which comprises applying a specific treating composition to the fabric, then pressing in the pleats, creases or the like, sewing the fabric into a garment or the like when so desired, and then curing the composition in situ. The specific composition is formed by reacting an aqueous formaldehyde-urea solution with urea under alkaline conditions, heating the mixture to a predetermined temperature, adding an alcohol at acidic pH, heating again to a predetermined temperature, neutralizing the pH of the mixture, stripping off the volatile matter, and then adding a loweralkylcarbamate to the residue and reacting further at an alkaline pH and at a predetermined temperature for a period sufficient to cause the reaction to go to completion. The essential step in this process is the addition of the loweralkylcarbamate as the last step. The term loweralkylcarbamate includes not only unsubstituted alkyls but such substituted lower alkyls as methoxy and hydroxyloweralkyl.

This invention relates to the treatment of fabrics, particularly of the wash-wear type, and of garments made therefrom, wherein, even after repeated launderings or dry cleaning, pleats, creases, or the like, applied to the fabrics during the process of manufacturing, are retained, whereas, wrinkles, creases, etc. appearing in the fabrics or garments after the completion of manufacture are removed during laundering or dry-cleaning.

The particular process in which the present invention is utilized is the so-called delayed-cure process wherein the treating composition, containing a resin finish, is applied to the fabric prior to its being made up into a garment, but wherein the composition is not cured until the garment has been completed and the required pleats, creases, or the like have been formed.

Heretofore, in delayed-cure processing, it was the general practice to employ as the resin finish either (a) a dimethylol-dihydroxyethyleneurea condensation product made from glyoxal, formaldehyde and urea, or (b) a uronresin formed by the reaction of urea, Formalin, paraformaldehyde and methanol, most frequently employed in the crude (undistilled) form, or (c) a so-called uron type resin formed by the reaction of a formaldehydeurea-solution and urea.

The aforementioned processes, however, had various disadvantages in accordance with the particular resin finish used. One such disadvantage was the excessive amount of obnoxious formaldehyde fumes in the uncured (and, often, even in the cured) fabrics because of the excessive amount of free formaldehyde present. This was particularly true of the so-called uron type resin. In order to avoid these fumes, it was necessary to repeatedly add water to the composition and to vacuum-distill-off this water and formaldehyde between each water addition. This continued heating, however, had the effect of forming appreciable amounts of undesirable polymerized resin which, in turn, produced a harsh, board-like effect on the hand of the treated fabric, especially, when the fabric contained synthetic fibers, such as nylon, polyester, Acrilan, acrylic fibers, and the like. The present process eliminates this necessity of repeated water-addition and distillation.

Another disadvantage of many of the prior processes was that the ratio of bound formaldehyde to urea in the resin, especially in the dimethylol-dihydroxyethyleneurea type resin, was undesirably low, i.e., no more than about 2:1. The greater the cross-linking effect caused by the reaction of the OH groups of cellulosic materials and bound formaldehyde, the better the wash-wear performance. In the present process, the resin finish has a ratio of bound formaldehyde to urea which is, generally greater than 2.5 :1.

Another great disadvantage of most prior processes was the yellowing that occurred when white or light-colored fabrics were cured. An important advantage of the present process is that it completely eliminates this yellowing effect while simultaneously retaining all the advantages of the prior type processes such as satisfactory tensile strength, tear strength, flex abrasion strength and wrinkle recovery. At the same time, the present process also provides a greatly improved (softer) hand.

The present process further provides high stability of the treated, but uncured fabrics, even when drying has been carried to extremely low moisture levels.

In accordance with the present invention, the essence of the improvement resides in the preparation of a uron type resin wherein, after the volatile matter has been stripped-off in vacuo, a solution of alkylcarbamate is added to the residue. Further reaction is then permitted to take place between the residue and the alkylcarbamate. The product resulting from this reaction is utilized as the resin finish in the present process.

The term alkyl carbamate, as used herein, includes both unsubstituted alkyl groups and such substituted alkyls as methoxyalkyl and hydroxyalkyl. The alkyl is also preferably a lower alkyl such as methyl, ethyl, propyl and isopropyl.

The following examples illustrate the present invention, with no intent, however, to limit the invention except as claimed:

EXAMPLE 1 Into a closed, agitated and jacketed reactor, equipped with vacuum distillation means, was charged the following:

Components: Parts by weight U.F. concentrate (an aqueous mixture containing, by weight, 60% formaldehyde and 25% urea-manufactured by Allied Chemical Co.) 3,330

Urea (solid) Aqueous NaOH, 25% strength (or sufficient to bring the pH of the mixture to about This mixture may be heated to a temperature of between about 50 to 90 C. for from about 1 to 3 hours. In this case, it was heated, with agitation, to the preferred temperature of about 70-80 C. for about 2 hours, after which 1,500 parts by weight methanol and 75 parts by weight 20 B. HCl were added, to bring the pH to between about 4.05.0.

The mixture was then heated under reflux (about 85 C.), and with agitation, for about 40 minutes (although the time may vary between about 15 minutes to 1 hour), after which it was neutralized and brought to a pH of about 8.5 with 25% caustic soda (about 100 parts by weight).

The volatile matter was then stripped off in vacuo (at about 28 inches) until the residue assayed about 70% by weight of dry solids.

To the residue was then added an 80% by weight solution of methoxyethylcarbamate in an amount equivalent to about 6% by weight, of the resin in the residue (although about 4 to 8% by weight may be used). The pH was then adjusted to about 10.0 and the reaction was then continued at about 50 C. for two hours.

At the end of the two hour period, the pH was adjusted to about 8.0 and the mixture was filtered.

Analysis of the final product revealed a total active content of 82% by weight, consisting of 77% by weight of dry solids and 4.9% by weight of free formaldehyde. The ratio of bound formaldehyde to urea was 2.71:1.

EXAMPLE 2 EXAMPLE 3 Into the same reactor as in Example 1 were charged the following:

Components: Parts by weight U.F.-85 concentrate 3,300 Urea 94 Aqueous NaOH, 25% strength (or suflicient to bring the pH of the mixture to about The mixture was heated, with agitation, to 210 F. After minutes, a vacuum of about 28 inches was drawn and as much water as possible (about 525 parts by weight) was distilled off. The mixture was then cooled to 90 F. and the vacuum was released.

There were then added about 1,650 parts by weight methanol and about 85 parts by weight B. HCl.

After about 40 minutes, the mixture was neutralized and brought to a pH of about 8.0 with about 100 parts by weight of NaOH, and the mixture was then vacuum stripped. At this time, the free formaldehyde content was about 12% by weight relative to the weight of the finished product which had a solids content of about 70% by weight. About 100 parts by weight of water was added, and the mixture was again vacuum-stripped under agitation. Five repetitions were required to obtain the required results as shown by analysis which revealed a total activity of about 81.3% by weight, of which solids constituted 76.5% and free formaldehyde 4.8%. The ratio of bound formaldehyde to urea was 2.05:1. The pH was then adjusted to about 8.0 and the mixture was filtered for clarification.

EXAMPLE 4 (A) A crude dimethyloluron dimethyl ether was prepared from urea, Formalin, paraformaldehyde and methanol by the method described in US. Patent No. 3,089,- 859. It contained 71% by weight of the uron.

(B) The crude uron was then distilled in vacuo at about 1 mm. pressure. The main cut assayed 98% by weight as dimethyloluron dimethyl ether.

(C) A portion of this distillate was then shaken with activated carbon and filtered for the purpose of decolorization.

In order to determine the relative softness or hand of fabrics treated with the present composition and those treated with prior type compositions, tests were run as in the following examples:

EXAMPLE 5 Mixed zinc-magnesium catalyst 5.5 40% active, reactive acrylic resin 2.5 Water 80.0

The term 40% active refers to the concentration of the resin in the product, while the term reactive means capable of cross-linking.

The samples were dried for 2 minutes at 250 F. and then cured for 10 minutes, at 340 F.

EXAMPLE 6 The same type fabrics as in Example 5 were treated by padding in the same bath as in Example 5 except that the product of Example 3 was substituted for the product of Example 1. These samples were then dried and cured in the same manner as in Example 5.

EXAMPLE 7 The treated samples of Examples 5 and 6 were evaluated for hand with the following ratings.

Exam- Fabrio ple 5 Example 6 Polyester/cotton Soft Full, hard. Rayon/acetate/nylon .d0 Very board-like. Acrilan/rayon/acetate do Board-like.

In order to determine color fastness and crease angle recovery, various tests were made, as in the following examples:

EXAMPLE 8 White 100% cotton broadcloth, and white 65/35 polyester cotton shirting were treated by padding in baths containing respectively the products of Examples 1 and 3 at the 16% level and the products of Examples 4A, 4B and 4C at the 12% level. Zinc nitrate catalyst was used in each case. All the samples were dried for 1 /2 minutes at 260 F. and then cured at 340 F. for 15 minutes.

cal brighteners or tints used in order that actual color changes could be observed. The results were as follows:

TABLE 1 A. White cotton broadcloth Crease angle recovery (deg) Color 290 Whitest. 284 Next whitest. 293 Much yellower. 285 Moderately yellower. 282 D0.

B. White 65/35 polyester cotton shirting Crease angle recovery (deg) Color 295 Whitest. 294 Next whitest. 292 Much yellower. 292 Moderately yellower. 294 Much yellower.

The crease angle recovery was obtained by means of the Monsanto crease angle recovery method (Method CCC-T19lB-52l2) hereinafter further discussed.

The fabrics made in accordance with the present invention (Example 1) are shown to be clearly superior to each of the other fabrics with regard to color fastness while the crease angle recovery was superior in every instance except one.

EXAMPLE 9 The following fabrics were padded on a one-dip, onenip, two rubber-roll padder at 40 tons pressure, at 80-90 F. utilizing the following bath composition:

(a) White, 100% cotton duck.

(b) Multicolor floral print, 100% cotton duck.

(e) White, 100% cotton sateen.

(d) Multicolor floral print, 100% cotton sateen.

(e) Natural, 50% polyester/50% cotton hopsacking.

The bath composition was as follows:

The samples were dried at 280 F. in a 45 foot gasfired, entirely-housed clip frame. The cotton sateens were run at 28 yards per minute, the cotton ducks and the hopsacking at yards per minute.

The sensitized (treated, but uncured) fabrics were then pressed on a Prosperity Press, Model #249MU, at 300 F. and medium pressure, programmed at 5 seconds steam, 15 seconds bake, and 5 seconds vacuum. The cotton fabrics were cured for 15 minutes at 325 F. while the polyester/ cotton fabric was cured for 10 minutes at 340 F.

EXAMPLE 10 Samples of the same fabrics as in Example 9 were padded in the same manner as in that example and under the same conditions, except that the following bath was used:

Bath composition: Parts by weight Permafresh 183- (-40% active dimethylol dihydroxy ethylene-urea condensation product-Warwick' Div. of Sun Chemical Co.) 22.0

40% active, reactive acrylic resin emulsion 2.0 30% active polyethylene emulsion 4.0 Zinc-nitrate catalyst 4.0

Water 68.0

The terms active and reactive have the same meaning as in Example 5.

The samples were dried in the same manner as in Example 9, except that the sateens were run at 30 yards per minute and the ducks and hopsacking at 28 yards per minute.

Pressing was carried out in the same manner as in Example 9. The cotton fabrics were cured for 10 minutes at 320 F. and the hopsacking for 10 minutes at 340 F.

Here, too, neither optical brighteners nor tints were used'in order that actual color changes could be readily observed.

In color fastness tests it was observed that the white fabrics treated with the composition of Example 9, when compared with untreated samples of the same fabrics, showed either no discoloration at all or just a very faint, hardly noticeable yellowing. The same fabrics treated withthe composition of Example 10, on the other hand, showed deep discoloration in every instance, this discoloration ranging from pale but quite noticeable yellow to almost brown.

. The colored fabrics treated in accordance with Example 9 showed no observable change of tint, whereas, the fabrics treated in accordance with Example 10 showed marked discoloration wherein the reds acquired a bluish to purplish cast, oranges and greens turned muddy, and blues became greenish.

The improved hand and color fastness of the fabrics treated in accordance with the present invention should also retain such desirable characteristics as satisfactory smoothness, tensile strength, tear strength and fiex abrasion, as compared with fabrics treated in accordance with the commonly used prior processes. It was found that fabrics treated in accordance with the present invention were, in most cases, at least as good and, in many cases, better than those fabrics treated in accordance with prior processes.

The testing methods used for these purposes were as follows:

(A) From the Federal Specification, Textile Test Methods:

(1) Tear strength-Method CCC-T-l91B-5l32 (2) Flex abrasion resistanceMethod CCCT-l91B (3) Monsanto crease angle recoveryMethod CCC-T- (B) From the 1964 Technical Manual of the American Association of Textile Chemists and Colorists:

(1) Crease retention rating-AATCC Method No. 88

(2) Wash/Wear ratingAATCC Method No. 88-B- (3) Flat frosting abrasionUnoflicial tentative method,

not yet printed.

(D) From the Westinghouse Electric Corporations Manual, Standard Home Laundering at 140 F. the Westinghouse Laundromat:

(1) Shrinkage, percent (E) From the American Society for Testing Materials, ASTM Standards on Textile Materials:

(1). Tensile strength, grab method-Method D-l682- All of the samples of the fabrics treated in Examples 9 and 10 were evaluated for smoothness, crease retention and shrinkage after one and five washings. The cotton ducks and the white 100% cotton sateen were tested for tensile strength, tear strength, flex abrasion and wrinkle recovery. The three printed fabrics were tested for fiat frosting abrasion. The following tables record the results. Unfinished material was used as the Control for the purpose of comparison. Wrinkle recovery was recorded as the sum of Warp and fill recoveries in degrees:

TABLE 2 A. 100% cotton duck-multicolor floral print Control Ex. 9 treatment Ex. 10 treatment Test Warp Fill Warp Fill Warp Fill Tensile strength (lbs) 108 54 83 30 72 25 Tear strength (grams) 1, 696 1, 408 2, 568 800 2, 176 736 Flex abrasion (cycles) 270 154 351 161 177 82 Wrinkle recovery (total W & F) 163 277 279 13. 100% cotton duck-white Tensile strength (lbs.) 111 69 70 36 64 27 Tear strength (grams).. 1, 952 1, 696 2, 016 960 1, 824 640 Flex abrasion (cycles) 164 86 287 101 91 34 Wrinkle recovery (total W & F) 169 293 287 G. 100% cotton sateen-white Tensile strength (1bs.) 47 88 36 50 34 39 Tear strength (grams) 1, 216 864 1, 024 704 736 512 Flex abraslon (cycles) 214 454 457 496 41 Wrinkle recovery (total W & F) 143 294 298 The following table is based on the Flat Frosting The following example illustrates the use of the present Abrasion Test utilizing 2.5 lb. head load and 1,200 cycles:

The wash/wear, shrinkage and crease retention characteristics of the fabrics of Examples 9 and 10 are listed invention in making a garment:

EXAMPLE 12 1n the following table: y Settlng thfi p TABLE 4 Percent Shrinkage Wash/W ear W/F Crease retention, Fabric Treatment I wash 5 wash 1 wash 5 wash 1 dz 5 wash Red/Cream 5. 0 5. 0 0. 5/0. 0 0. 5/0. 0 5 cotton duck. 5.0 5.0 0. 5/1. 0 0. 5/1. 0 5 White cotton 4. 4 4. 1 0. 5/0. 5 1.0/0. 5 5 duck. 4. 5 4. 3 0. 5/0. 0 0. 5/0. 5 5 White cotton 4. 5 4. 1 0. 0/0. 5 0. 5/1. 0 5 sateen. 4. 5 4. 1 0. 0/0. 5 0. 0/0. 5 5 Blue] Green 5. 0 4. 7 0. 0/0. 0 0. 5/0. 5 5 cotton sateen. Ex. 10 5.0 4. 7 0. 5/0. 5 0. 5/0. 5 5 Red/Green Ex. 9 5.0 5.0 0. 0/0. 5 0. 5/1. 0 5 cotton sateen. Ex. 10.. 5. 0 5. 0 0. 0/1. 0 0. 0/1. 0 5 Poly/cotton Ex. 9.-- 4. 7 4. 3 0. 5/0. 5 1. 0/0. 5 5 hopsacking. Ex. 10 4. 5 4. 3 1. 0/0. 0 1. 0/0. 5 5

The above table indicates that the wash/wear, shrinkage and crease retention of the fabrics treated in accordance with the present invention (Example 9) are, generally, as good as those treated in accordance with prior processes.

In order to determine the storage characteristics of the fabrics treated in accordance with the present invention, the following test was run, as in the following example:

EXAMPLE 11 The completed garment was, thereafter, laundered in a washing machine, at F., using Tide detergent, for a full machine cycle, after which it was tumble-dried. The garment retained its pleats unwrinkled, and the seams remained unpuckered.

The invention claimed is:

1. A process of making a composition for treating fabrics to make them press-free which comprises reacting an aqueous formaldehyde-urea mixture wherein the amount of formaldehyde exceeds the amount of urea, with urea at a temperature of about 4090 C. for about 1 to 3 hours, while maintaining the pH of the mixture greater than 10.0, to form methylolated urea and its low polymers, then adding an amount of a lower aliphatic alcohol in excess of the amount required to etherify the methylol groups on the acid side, while maintaining the pH at about 4.0-5.0, by the addition of an acid, there after agitating the mixture at reflux temperature for about 15 to 60 minutes, followed by neutralization and the addition of an alkali to bring the pH to about 8.5, thereafter stripping off the volatile matter, then adding an amount of loweralkylcarbamate wherein the alkyl contains less than 4 carbon atoms, equivalent to about 4.0

to 8.0% by weight of the solids content of the residue, References Cited and adjusting the mixture to a pH of about 10.0 while UNITED STATES PATENTS maintaining the mixture at a temperature and for a tlme suflicient to substantially complete the reaction between $063,869 11/1962 117 139-4 said residue and the loweralkylcarbamate. 5 3,089359 5/1963 m XR 2. The process of claim 1 wherein the loweralkylcarba- 3,369,858 2/1968 P et a] 117-1394 XR mate is a member of the group consisting of unsubstituted 3,378,397 4/1968 Sllvestrl et 117 139-4 loweralkylcarbarnate, methoxyloweralkylcarbamate and 3,381,310 5 1968 Tesoro et a1 117139-4 XR hydroxyloweralkylcarbamate- DAVID KLEIN, Primary Examiner 3. The process of claim 1 wherein the loweralkylcarba- 10 mate is methoxyethylcarbamate. US. Cl. X.R.

4. A composition made by the process of claim 1. 117-139.4; 2528.8 

